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Maldonado 1
Maldonado 1
Francisco Jos
Jos Maldonado Hdar
Dpt. of Inorganic Chemistry
University of Granada. Spain.
Email: fjmaldon@ugr.es
Phone: +34 958240444
Contents
1. Introduction: the importance of catalysis and some historical data.
2. Concepts:
- Catalyst
- Activation energy
- The catalytic cycle
3. The catalyst selection
4. Heterogeneous catalysis and surface science
- Structural consideration
- Surface and adsorption
Contents
5. About the active sites of surfaces
- Relationships of crystal defects and catalytic activity
- The nature of the crystallographic layer
- The geometric factor
- Bi - functional catalysts
- Acid sites in zeolites
- Electronic properties
6. Catalysts preparation:
- Bulk catalysts
- Supported catalyst
7. The catalysts deactivation / regeneration
3
Introduction
4
Raw materials
Catalyzed processes
Valuable products
Environmental
Catalysis
6
What to know ?
There is no a single theory of heterogeneous catalysis, but only a
series of principles to interpret and predict the processes that
occur, mainly in the gas solid interface.
Oxidoreductases
Transferases
Hydrolases
Lyases
Isomerases
Ligases
Among the first industrial catalytic processes are a few inorganic oxidation processes,
as the Deacon process (HCl into Cl2) and the production of sulfuric acid. The
production of sulfuric acid was commercialized in the mid-18th century. In the socalled lead chamber process the oxidation of SO2 into SO3 was catalyzed by NO.
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Concepts
11
What is a catalyst?
The name 'catalysis' was coined by Berzelius in 1836. He concluded that besides
'affinity' a new force is operative, the 'Catalytic Force'. With this, try to focus the
behavior of some substances that permit initiate reaction of decomposition or
synthesis. At that time no understanding existed, on a molecular level, of
reaction rates.
Definition of catalyst
According to the IUPAC (1976) a catalyst is a substance that, being present in
small proportions, increases the rate of attainment of chemical equilibrium,
without itself undergoing chemical change.
Comments
- This means that catalyst is not a reactant (is not consumed by the reaction)
- In fact, catalyst undergoes transitory changes to catalyze the reaction, and
permanent changes which typically leads to the catalyst deactivation
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Types of catalysts:
Catalytic processes can be divided in three main types: heterogeneous
homogeneous and enzymatic processes.
In a heterogeneous reaction, the catalyst is in a different phase from
the reactants. Normally, the catalyst is a solid and reactants are fluids (liquids or
gases). It is characterized by the presence of active sites on the catalyst surface.
In a homogeneous reaction, the catalyst is in the same phase as the
reactants (as the hydrolysis of esters by acid catalysts, all reactants and catalyst
are dissolved in water:
H+
CH3CO2CH3(aq) + H2O(l)
CH3CO2H(aq) + CH3OH(aq)
The enzymatic catalysis (biocatalysis) have an intermediate character
between homogeneous and heterogeneous processes, because although the
enzymes and reactants are in the same phase (solution), they have active sites
in their structures.
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(R = reactant, P = Product)
where the reaction rate is null or negligible, the use of a catalyst (C)
provide a new reaction pathway trough the formation of an
intermediate specie on the catalyst surface
R
R+C
RC
RC
P+C
RC
P
Activation Energy
Activation Energy : The energy required to overcome the reaction
barrier. Usually given a symbol Ea or G
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Activation Energy
G0
c o n v e rs io n
This
means
that
all
the
thermodynamic parameters, including
the equilibrium constant
K = exp (- G0 /RT)
equilibrium
without catalyst
with catalyst
Time
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Desorption of reaction
products (v)
adsorption (ii)
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Steps of reaction
(i, ii) diffusion and adsorption
If no diffusion restriction occurs, one or more of the reactants are
adsorbed on to the surface of the catalyst
Be careful!
Adsorption is where something sticks to a surface. It isn't the same as
Absorption where one substance is taken up within the structure of
another.
Differences between physisorption and chemisorption will be analyzed
before.
10
A2 + 2 B = 2AB
Eley-Rideal mechanism:
Langmuir-Hinshelwood mechanisms
A2 + * = A2*
A2* + * = 2A*
A* + B = AB + *
A2 + * = A2*
A2* + * = 2A*
B + * = B*
A* + B* = AB* + *
AB* = AB + *
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Eley-Rideal or Langmuir-Hinshelwood?
For the Eley-Rideal mechanism:
the rate will increase with increasing coverage until the
surface is completely covered by A*.
For the Langmuir-Hinshelwood mechanism:
the rate will go through a maximum and end up at zero,
when the surface is completely covered by A*.
This happens because the step
B + * = B*
B + * = B*
requires a free site.
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11
(iii, iv) The adsorbed species can move, interacting between them and
with the catalyst surface and reaction happens through the formation and
decomposition of an intermediate adsorbed specie.
At this stage, both of the reactant molecules might be attached to the surface,
or one might be attached and hit by the other one moving freely in the gas or
liquid.
The mobility of chemical species on the catalyst surface is also noticeable,
phenomena such the spillover of hydrogen atoms play an important role in
hydrogenation reactions.
The apparition of bonds or interactions with the catalyst surface debilitates or
destroys the intra-molecular bonds, inducing the reactions.
(v) The product from the decomposition of the intermediate specie should
be desorbed and diffuse in the flow.
Desorption simply means that the product molecules break away. This leaves
the active site available for a new set of molecules to attach to and react. 23
Example:
The hydrogenation of a carbon-carbon double bond
CH2 = CH2 + H2
CH3-CH3
Ni
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12
Ethene molecules are adsorbed on the surface of the nickel. The double
bond between the carbon atoms breaks and the electrons are used to bond it
to the nickel surface
Hydrogen molecules are also adsorbed on to the surface of the nickel. When
this happens, the hydrogen molecules are broken into atoms. These can move
around on the surface of the nickel.
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As before, one of the hydrogen atoms forms a bond with the carbon, and that end
also breaks free. There is now space on the surface of the nickel for new reactant
molecules to go through the whole process again.
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13
27
Non-chemical
Activity
Morphology
Selectivity
Mechanical strength
Cost
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14
Ri
T, P, flow
Rf + P1 + P2
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15
Ri
Conversion (%)
Rf + P1 + P2
T, P,
flow
T1
T2
Time on stream
Conversion (%)
R1
T1
T2
Time on stream
Product
s
16
this rate coefficient (K) will change as the prevailing conditions of the reaction
vary, and it is convenient to use the Arrhenius equation:
33
Turnover frequency
Far more convenient is the use of the concept of turnover frequency or turnover
number. The turnover frequency (often designated TOF) is simply the number
of times n that the overall catalytic reaction in question takes place per catalytic
site per unit time for a fixed set of reaction conditions (temperature, pressure or
concentration, reactant ratio, extent of reaction).
It is sometimes difficult to
determine the number of active
sites. For such situations, S is
often replaced by the total,
readily measurable, area A of
the exposed catalyst.
Note that TOF is a rate, not a rate coefficient, so that it is necessary to specify
all the prevailing conditions of the catalytic reaction.
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17
T, P, flow
Rf + P1 + P2
Heterogeneous catalysis
and Surface Science
36
18
Heterogeneous Catalysts is a
Surface Science!!!
The catalytic processes develops ONLY on the catalyst surface.
Therefore, the catalyst surface should be as large as possible,
but moreover, surface must be accessible to the reactants.
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Surface heterogeneity
19
Adsorption is brought about by the interactions between the solid and the
molecules in the fluid phase. Two kinds of forces are involved, which give rise to
either physisorption or chemisorption.
Physisorption forces are mainly dispersion and van der Waals attractive forces,
which do not depend on the polar nature of the adsorbent or adsorptive and are
therefore regarded as non-specific, whereas chemisorption interactions are
essentially responsible for the formation of chemical compounds.
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20
Physisorption
Ea for
chemisorption
Chemisorption
distance
Heat of physisorption
Heat of chemisorption
Physisorption
Chemisorption
Adsorbent
All solids
Some solids
Adsorbate
All vapors
Some gases
Temperature
Low
High
Amount adsorbed
High
Low
Low
High
High
Low
Specificity
Reversibility
Reversible
irreversible
Heat of adsorption
Low (0.5(0.5-5
Kcal/mol)
Surface coverage
multilayer
monolayer
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21
Reactions
Catalytic phases
Metals
Hydrogenation
/dehydrogenation,
oxidations, hydrogenolysis
NiO,
NiO, ZnO,
ZnO, MnO2,
WS2, MoS2
Stoichiometric
oxides
Polymerization,
Isomerization, cracking,
alkylation
The crystalline structure of the catalyst will define the catalytic active surface
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22
Structure of metals
Metal present only three main structures. Most of them (71%) adopt a packing
arrangement which maximizes the occupation of space: ccp or hcp.
Alternatively, alkali metals and some transitions metals present bcc structure.
45
Structure of metals
The compact layers are packed with a
sequence ABAB leading to the
hexagonal
(hcp)
structure,
or
ABCABC, leading to the cubic (ccp or
fcc) structure.
hcp
ccp
23
D = 0.414r
D = 0.225r
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Hole distribution
The interstices also form layers between the atom layers, located at d
Td+ d Oct and d Td-. The occupation of these holes will
determine the structure of metal compounds.
24
Structure of metals
BCC structure
hcp, C.N =12
bcc, C.N = 8
BCC
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25
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26
Structural effects
Schematic diagram of product shape selectivity: Para-xylene
diffuses preferentially out of the zeolite channels
54
27
Careful
thermodynamic
measurements leave no
doubt about the existence
of
numerous
nonstoichoimetric materials of
general formula TinO2n-1
and VnO2n-1
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Miller indices
Planes in a crystallographic
structure are labeled using
Miller indices
Calculations:
i)
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29
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Substitutional defects
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30
Substitutional defects
But substitional defect also produce strong changes in the conductivity of the solids:
P+e
When Ge structure is doped with P or As, which have five valence electrons,
four of them are shared with germanium atoms forming covalent bonds,
while the fifth becomes quasi-free. This type of impurities is known as a
donor impurity and it confers n-type semiconductivity.
On the contrary, when Ge is doped with B, Ga or In, each trivalent impurity
atom accommodated, there would be one positive hole formed into the
valence band. This type of impurity is known as an acceptor impurity and it
confers p-type semiconductivity.
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linear defects
Screw dislocations
Edge dislocations
Edge dislocations are caused by the termination
of a plane of atoms in the middle of a crystal
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Boundaries are regions of high energy, and consequently, with strong interactions
with the environment.
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2N2O
== 2N2 + O2
Followed by
2 O- == O2 + 2 e (to catalyst)
Or by
O- (ads) + N2O == N2 + O2 + e
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32
insulator
n type semiconductor
Activity
The activity of different metal oxide in this reaction can be divided into three
group: p-type semiconductor, insulator, n type semiconductor. The most
active catalyst are p-type semiconductor.
It is assumed that the slow step is:
2 O- == O2 + 2 e (to catalyst)
If this transfer of electrons is the slow step, the
higher activity of p-semiconductors is related
with their lower lying energy levels.
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33
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catalytic activity
The crystal defects are the genesis of the active sites concept, associated to
chemisorption sites, but remember that strong chemisorption avoid the
reactions and deactivates the catalysts by blocking the active sites.
weak
adsorption
strong
adsorption
Hf (Kcal/mol)
Volcano plots
68
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70
35
71
36
There is one acid hydrogen for every tetrahedrally bonded aluminium. These
active sites are distributed uniformly throughout the bulk and are bridging hydroxyl
groups. These are the classic Bronsted acid sites, the intrinsic strength of which is
a function both of the particular local environment and also the Si/Al ratio.
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ii)
Hydrolysis of ion-exchanged
polivalent cations followed by partial
dehydration
M (n-1)+Z- + H+Z74
37
76
38
77
A. NH3 (Lewis base) coordinately linked to Al+3 ions (Lewis acid) on Al2O3 surface. B and
C. Linear and bridge adsorption of CO on Pt. D and E. Dissociative adsorption on Pt of H2
or alkanes. F. Dissociative adsorption of N2 on Fe. G. Heterolitic dissociative adsorption of
H2 on the ZnO surface. H. Adsorbed complex with charge transference. I. Adsorption of isobutene on silica alumina where the acid surface proton (-OH) was transferred to the
isobutene. J and K. Possibilities of ethylene adsorption on Pt. L. Adsorption of O2 on metal
oxides with charge transference. M. Dissociative adsorption of O2. N. Heterolitic dissociative
78
adsorption of propylene on ZnO.
39
Preparation of catalysts
Types of solid catalysts
80
40
81
Bulk catalysts
Supported catalysts
41
Bulk catalysts can be prepared from two routes, precipitation is the most
common but a small number of heterogeneous catalysts is prepared by the
fusion of mixtures of oxidic or metallic precursors.
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84
42
85
86
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87
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45
One of the advantages of the sol-gel process is the flexibility of the process, that
permits to obtain catalysts in different configurations by templating or coating methods.
91
Supported Catalysts
Many industrial catalysts consist of metals or metal compounds finely dispersed
on an appropriate supports.
The role of the support is not merely that of a carrier; it may actually contribute
catalytic activity. Further, the interaction between the active phase and the
support phase can affect the catalytic activity.
Ni supported on SiO2
46
93
94
47
95
Zeolites
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97
98
49
100
50
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MERCURY POROSIMETRY
Mercury porosimetry is used for the determination of the pore volume and
the size distribution of meso- and macropores.
The technique uses progressive increase of the external pressure to force
mercury into the pores of the sample studied. An inverse relationship exists
between the pressure applied P and the pore radius rp. For cylindrical pores
this is the Washburn equation:
103
104
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Supported Catalysts
The concept of dispersion
The degree of dispersion, defined
by the ratio of the number of
surface atoms to the total number
of atoms in the polyhedron under
consideration, NS/NT.
Dispersion needs to be as close as
possible to unity so as to maximize
the utilization of a catalyst.
For very small clusters it is not
crystallographically sensible to talk of
planes with Miller indices. Small particles
may not be favorable when the reaction is
structure-sensitive, and larger particles
may exhibit a higher activity and/or
selectivity per unit surface area.
Supported Catalysts
The procedures used to prepare supported catalysts can be divided into two
main groups:
(i) the selective removal of one or more component of usually non-porous
bodies of a compound containing precursors of the support and the active
component(s);
(ii) the application of a precursor of the active component(s) onto a separately
produced support
Bulk catalysts
Supported catalysts
106
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Supported Catalysts
The procedures used to load separately produced supports are:
-
107
108
54
110
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Exhaust gas
from motor
Purified
Exhaust gas
Ceramic
Monolithic
Support
111
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113
Catalyst deactivation
The activity and selectivity of heterogeneous catalysts may change during the
course of reaction. Usually activity decreases due to either chemical or physical
reasons, or a combination both factors.
However, sometimes the selectivity increases, and therefore, is not to be viewed
as an entirely negative effect.
114
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Catalyst deactivation
Catalyst deactivation can be caused by:
(i) a decrease in the number of active sites
(ii) A decrease in the quality of the active sites
(iii) degradation of accessibility of the pore space
The main causes of deactivation can be classified as:
115
Catalyst deactivation
Poisoning:
58
Catalyst deactivation
Formation of Deposits
The formation of deposits can be of a physical or a chemical
nature.
So-called catalyst fouling is a physical process, which covers all phenomena in
which material is deposited on the surface of the catalyst to block active sites
and/or pores.
In most cases, the catalyst causes the formation of
undesired by- products that lead to deposits. The most
commonly encountered is so-called coke, which is
formed by chemical reactions of hydrocarbons at
relatively high temperature.
When large amounts of coke are deposited, the
diffusion characteristics change as a result of narrowing
or even complete blocking of the catalyst pores.
117
Catalyst deactivation
Thermal Degradation
Thermal degradation is a physical process leading to
catalyst deactivation because of high-temperature-induced
sintering, chemical transformations, evaporation, etc.
Sintering
59
Catalyst deactivation
Thermal Degradation
Sintering resembles crystallization: larger
particles grow at the expense of smaller
ones. Particles might move and coalesce
or atoms move from one particle to
another, either by volatilization or by
surface migration.
The position of the particle contributes to the ease of sintering. A valley position
is stable, whereas an on-top position is highly unstable.
Catalyst deactivation
Thermal Degradation
Chemical transformations,
Evaporation,
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60
Catalyst deactivation
Mechanical Deactivation
Mechanical strength is important in giving the catalyst
resistance against crushing. In a fluidized-bed reactor,
attrition will always occur and the fines formed will be carried
away with the product flow.
The shape and porosity of the catalyst particles influence mechanical strength: a
spherical shape is most favorable, while the higher the porosity, the lower is the
mechanical strength. In particular, macropores will lead to reduced strength.
In washcoat monoliths, the adherence of the coating to the monolith is very
important. The washcoat may be fractured and/or separated from the monolith
because of thermal stresses.
This is particularly relevant in automotive applications, in which the catalyst is
subject to a wide range of temperatures that change very often and very rapidly
(engine on off).
121
Catalyst deactivation
Corrosion / Leaching
Particularly in liquid-phase catalysis, leaching of the active metal by
dissolution into the surrounding liquid reaction mixture is often a
concern.
In most cases, leaching is the result of solvolysis of metaloxygen
bonds through which the catalyst is attached to the support. This not
only causes loss of catalyst activity, but also results in contamination of
the product.
The support material itself may be also subjected to leaching. The
reaction medium can be corrosive. Consider alumina at high or low
pH. Above pH 12 it will dissolve.
122
61
Catalyst deactivation
Summary
124
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What To Do?
When poisoning is the problem, a more robust active phase or support
might be selected. Example: Alumina forms a surface sulfate with sulfur
oxides, whereas titania is inert.
When fouling is the problem, the option is to optimize the catalyst texture
(wide / narrow pores). The coke deposition can be prevented by tuning the
reaction conditions or by alloying the metal particles.
Sintering is more easily prevented than cured, as it is often irreversible.
Sintering can be reduced by structural promoters or stabilizers. Example,
the addition of Re to the Pt/alumina catalyst leads to strongly improved
stability.
The crushing strengths and attrition resistances of catalysts can be
significantly improved, for example by using different preparation or
shaping methods
125
What To Do?
It will be clear that the time-scale of deactivation influences the choice
of reactor type, the mode of operation and regeneration.
With increasing the deactivation rate, the choice of the reactor type
changes from fixed bed to the riser with continuous regeneration.
The correct choice of the operating conditions strongly influences the
catalyst life, which vary from years to days.
126
63
127
In spite of the increasing price and demand of noble metals (platinum group,
PGM) the real recycling degree only reach about 30% of the potential
128
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132
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